Triazine fluorescent agents



Patented Jan. 12, 1954 UNITED STATES PATENT OFFICE TRIAZINE FLUORESCENT AGENTS No Drawing. Application January 26, 1951,

Serial No.

6 Claims. 1

This invention relates to novel fluorescent agents derived from diamino-stilbene sulfonic (or carboxylic) acids which are of particular value as optical bleaching particularly for incorporation in soaps and other detergents.

The novel fluorescent agents of the present invention may be represented by the following general formula:

i -H 4 3\ N 2CNH CH= W- C Fa 2 Formula I wherein the group Y\ /X N represents NH2 or the residue of a primary or secondary amine, for instance, if X is Y may be H, alkyl or substituted alkyl such as CH3-, C2H5, (CH3) 2CH-, n--C4H9, sec. C4H9-, -C12H25, -CH2CH2OH, -CH2O-H, etc., aryl such as CsHs, C1C6H4, CHsCeH4, CH3OCsH4-, CF3CsI-I4-, C1oH'1- (naphthyl), C14H9 (anthracene), HOaSCsI-I4-, (CH3)2C6H3, etc., heterocyclic such as thiazole, benzothiazole, tetrazole, etc., alicyclic such as cyclohexyl, tetrahydronaphthyl, etc. while if X is alkyl or substituted alkyl such as methyl, ethyl, propyl, hydroxyethyl, methylol, etc., Y may be alkyl or substituted alkyl such as CHs-, C2H5, C3111, C4H9, C'H2OH, CHZCHZOH, etc., aryl residues such as CsH5-, ClCsH4, CH3OCsH4'-, CHsCsI-Ir, CH7, etc. and heterocyclic such as thiazole, pyrimidine, benzothiazole, etc. and finally X and Y together may go to form cyclic residues such as pyrimidine, morpholine, thiomorpholine and W represents hydrogen, alkoxy, aryloxyl, halogen, cyano, trifluoroalkyl, Z represents the group -C'OOM or SO3M in which M represents hydrogen or a cation, usually alkali metal (i. e. sodium or potassium) or ammonium, alkylol amine, etc., or alkaline eart metal such as barium or calcium.

These novel compounds are readily prepared by first condensing a4,4-diaminostilbenesulfonic or carboxylic acid usually 4,l'-diamino2-stil benedisulfonic acid (although other 4,4'-diaminostilbene acids such as 4,4'-diaminosti1bene 3,3- disulfonic acid, 4,4'-diaminostilbene-2,2,6,6'- tetrasulfonic acid, 4,4'--diaminostilben.e-2,2'-dicarboxylic acid, or 4,4-diaminostilbene-3,3'-dicarboxylic acid may be used if desired) with cyanuric chloride; 2 molar proportions of cyanuric chloride (or pro-mide) being employed for each molar proportion of 4,4-diaminostilbene-2,2'-disulfonic acid. The thus obtained primary condensation product is then further condensed with 2 molar proportions of an aminobenzotrifiuoride, usually 3 aminobenzotrifluoride although the 2'- or i-aminobenzotrifluorides and their alkoxy, aryloxy, alkyl, halogen, cyano and trifluoroalkyl derivatives may be used if desired, as examples thereof may be mentioned l-amino-2-methoxy- S-trifiuoromethylbenzene, l-amino-2-(p-chlorophenoxy)-5-trifluoromethylbenzene, l-amino-Z- o-tolyloxy-5-triiluoromethylbenzene, 3-:amino-4- chlorobenzotrifiuoride, 2-chloro-5 aminobenzotrifluoride, 3-amino-4-cyano-1-trifiuoromethylbenzene, 3-5-bistrifluoromethylaniline, whereby there is obtained .a novel intermediate product having the following formula:

Formula II 2 wherein X stands for chlorine or bromine and W and Z are as defined above.

This novel intermediate product is then finally condensed with 2 molecular proportions of ammonia or a primary or secondary amine in order to obtain the novel products of the present invention.

These condensations may be carried out by procedures commonly employed in the art for affecting such condensations. In order to fully illustrate the preparation of compounds of present invention the following detailed illustrations of the preparation of the novelintermediate of the present invention and of specific fluorescent intermediate of Formula II above (in which X agents embodied therein are given. The parts are is chlorine, W is chlorine in G-position, CF3 is by weight. in 3-position and Z is in Z-position and represents SOaI-I) in the form of the free acid.

These above products are themselves fluorescent agents but do not have outstanding prop erties as such and are therefore preferably fur- 3'? parts of cyanuric chloride are dissolved in ther condensed with ammonia or a primary or 120 parts of acetone and poured into a mixture secondary amine to produce the improved fluoof ice and water. During the suspension in the rescent agents of this invention. This condensaioe water the temperature of the aqueous suspention is readily affected by adding approximately sion should not rise above 5 C. 37 parts of 4,4'- 2 mols of ammonia or a primary or secondary diaminostilbene-2,2-disulfonic acid are dissolved amine to the mixture of a novel intermediate in 150 parts of water with the addition of enough product obtained as described above, without sodium carbonatetogiveaneutral solution. This purification. There is also added a suii'icient solution is then added slowly to the cyanuric chloamount of alkali such as sodium carbonate in ride suspension in ice water and at the same time order to increase the pH of the solution to 7.5 a solution of sodium carbonate is slowly added in to 8 and the mixture is heated to temperature order to keep the mixture from becoming too acid of about 90 C. until the condensation is com- (pH of 8 to 8.5). During this addition and conplete. The novel products of the present invensequent condensation the temperature should not tion may then be isolated in the usual manner. rise above 5 C. The condensation of the cy- EXAMPLE In anuric chloride with the diaminostilbenedisulionic acid is complete when a sample of the re- The novel intermediate products obtained as action mixture which has been acidified and described in Examples I and II are each mixed treated with sodium nitrite does not develop color with 25 parts of morpholine and the pH of the when treated with analkaline solution of H solution is increased to 7.5 to 8.0 by the addition salt. of sodium carbonate solution. The thus formed When this condensation is complete a solution mixtures are heated slowly to 90 C. and mainof 32.2 parts of 3-aminobenzotrifluoride is added tained at that temperature for 3 hours. The to the thus obtained product and immediately mixtures are then cooled and the products isoafterwards a solution of 160 parts of anhydrous lated in the usual manner. sodium acetate in 400 parts of Water is added. The product obtained from the intermediate The thus obtained mixture is allowed to warm of Example I has the following formula:

Preparation of intermediate 5 EXAMPLE I The product obtained from the intermediate of Example II has the following formu1a:

to room temperature and may be heated to to C. if necessary to complete the condensa- CH2CH2 CHz-CH: I

o N N 0 CHI-on, C-N NC- om-o1au x N\ /CHN CH=CHONHC\ /N l V N=O I OaNa NaO S NH NH V 1 Cl- 7 C1 CF; CF:

tion. Thus there is obtained the novel interme- EXAMPLE 1v diate of the Formula II above (in which X is i i o iti n itt z lil zfioiliifi ifia regilefits fs sis in chimed as deserved, Examples 1 and the form of the free acid. there ls ad ded 25 parts of dlethanolamme nd 1 the pH is increased to 7.5 to 8 by the addition EXAM II of sodium carbonate solution and the mixtures The procedure of Example I is followed except slowly heated to 90 C. and maintained at this that 39 parts of 3-amino-4-chlorobenzotrifluoride temperature for 3 hours. The mixtures are then are used in place of 32.3 parts of 2 aminobenzocooled and the products isolated in the usual trifluoride. Thus there is obtained the novel manner.

To each of the novel intermediate products 6. The product obtained from the novel inter: related products which contain no aminobenzm mediate of Example I has the following formula: trifluoride radical. HOH4C2 CzH OH T B05402 /O=N /N-C\ 02114011 N C-HN-OH=OH-ONHC/ \N C-N A l N=C OaNll NaO S I r e -o F3 m j The product obtained from the novel interme- As examples of amines which may be condensed diate of Example II has the following formula: with the intermediate of Formula II above to,

Home: olHloH r Hormel /C=N\ N=o 'olH o N CHN-CH=CH-NHC N oN N-C SOaNB. NaOaS I r m NH Cl- C1 0 F3 -CF3 EXAMPLE V produce valuable fluorescent agents of Formula To the novel intermediate product obtained as I above in which the group described in Example I there is added 32.2 parts Y X of 3 aminobenzotrifluoride and the pH is increased to 7.5 to 8 by the addition of sodium carbonate solution and the mixture slowly heated will correspond to the amino radical of the par-. to 90 C. and maintained at this temperature for ticular amine employed may be mentioned pri- 3 hours. There is obtained on cooling of the reacmary alkyl amines such as methyl-, methylol,

tion mixture and isolation in the usual manner ethyl-, ethylol, propyl-, isopropyl-,n-sec.- or tert.-

a compound corresponding to the formula: butyl-, dodecyl-, or stearyl-amino etc.; primary CFa I O Na OaNa When the above-materials (the products of aryl amines such as chloroanilines, toluidines, mp I V a V) a incorporated i anisidines, xylidenes, naphthylamines, anthryldischarge p s d applied to fabrics n the amine, p-sulfonic aniline, 3-amino phenol etc., u ua manner. the Whites thus obtained were also heterocyclic amines such as Z-aminothiazole,

i noticeably whiter than those using ordinary disg i b th 2 amino pyrimidine etc" charge P When the mat-enals apphed also cycloalkyl amines such as cyclohexyl amine, to fibers of cellulose, wool and nylon by methods tetrahydronaphthyl amine, etc., also alkaryl amines such as benzylamine, etc. As example of secondary amines which may be used may be L well known in the art, the white appearance of the fabric was thereby much improved. When small amounts of these materials are added to soaps and synthetic detergents and the resulting i i f secondary lammgs 80.1 gf g mg mixture employed to wash fabrics, white materials 0 0 e a We p-nmaly ammes m w w an thus washed are extraordinarily whiter in ap ammo hydrogen a been replajced by an pearance and colored materials brighter than or heterocyfihc group, for mstanced1a1ky1 similar materials which are washed using ordiammes such as dlmethylw iethy-1-, methyl ethyl, nary soaps or detergents. It has also been found dibutyl'i -Y methylbutylw mothyloyclothat the novel fluorescent agents of the present hexylaminos, also y a yl a ines Such as invention not only have every good whitening y 'u N-butylonilinos. eiTect, but this effect is faster to hypochlorite dines, -naphthylamines, -aminothiazoles, -aminobleach and to light than the efiect obtained from pyridines etc., also such heterocyclic sec y calcium salts which may be obtained'from the free acid or by double decomposition of the sodium or potassium salts have been found to be useful for the brightening of photographic prints etc.

In addition to the specific fluorescent agents described above it hasbeen found that the novel products represented by the general Formula I amines as carbazole, thiomorpholino, pyrrole pyr rolidino indole etc.

A number of derivatives of the type indicated above of 4,4 bis[4 amino 6 aminobenzotri fluoryl-2-5-triazinylaminol 2,2 -'stilbenedisul- 5 fonic acid and its salts have been prepared and it has been found that the compounds ofthe present invention which in the 6-position of the above and which may be obtained by condensing triazyl ring contain a substituent and in 4-posithe novel intermediate represented by Formula II liion of the triazyl ring ta a ami o sub- 10 above with awide variety of primary and secondstituent are desirable fluorescent agents and are ary amines are also valuable fluorescent agents. superior to known fluorescent agents of the same The novel fluorescent agents of the present ingeneral type; i. e. which contain no aminobenzovention fluoresce under ultra-violet light with a trifluoride substituent in the triazyl ring but inbluish fluorescence, and since they are substanstead contain other amino, hydroxy substituents tive to cellulosic materials, are particularly valuand the like. It is therefore believed that the able for incorporation into soaps and synthetic nature of the amino substituent in l-position is detergents such as alkyl aryl sulfonates, higher not highly critical and that substantially any fatty acid methyl taurides, non-ionic detergents primary or secondary amine, as well as amsuch as the polyglycol ethers of alkyl phenols or monia, may be condensed with the novel interof partial higher fatty acid esters of mannitol mediate of the present invention to producevaluor sorbitol. The fabrics washed with formulaable fluorescent agents. It is, however, preferable tions of detergents containing these fluorescent that the amino substituent in 4-position in the a nts appear much whiter in the case of Whites triazyl ring contain no groups such as free amino and much brighter in the case of colors than or hydroxy groups etc. which as a usual rule have fabrics which are washed with ordinary soaps or an adverse effect on the light and chlorine fastdetergents Those fluorescent agents y a ss of th fluorescent t be applied to fabrics by separate treating baths It will be apparent that in the foregoing exand similar methods and p e s Well k own amples the novel products of the present invenin the y are also useful When p tion were obtained in the form of their sodium rated into paper or other wrapping materials, salts. However, the potassium salts have subparticularly oellulosio W pp m terial to imstantially similar properties and it will b a prove the whiteness of such material} as w'ellas parent that the potassium salts will be obtained to protect the contents from the action of ultraby using potassium carbonate and acetate in Violet light- They y so be in rporat d in place of sodium carbonate and acetate as the discharge pastes whereby the whites obtained alkaline agents for the condensations in the synp discharge re ecid y Whiter than those thesis of these materials. The free acids may be discharges made in the absence of such maobtained by acidification of the sodium or poterials. They may also be used to bleach fabrics tassium salt while other salts such as the amand in such cases the amount of bleach necessary monium or alkylol amine salts may be obtained is materially reduced and one or more steps of by neutralization of the free acids. Where spirit the normal bleaching operations may b li soluble products are desired, for instance, in nated. v brightening of lacquers etc. the higher alkyl or We claim: a cycloalkyl amine salts of the free acids such as 1. Fluorescent agents which inthe form of the the cyclohexyl amine salts of the free acids may 45 free acids have the formula be produced by methods known in the art. The V 2. Fluorescent agents which in the form of free alkaline earth metal salts such as the barium and acids have the formula 0 Hz-C H2 7 C Hr C Hi 1 o N N O CHzC2 \CN 0 o111o,

-' L or,

3. Fluorescent agents which in the form of free wherein A represents a member of the group conacids have the formula sisting of chlorine and bromine and primary H0 H4 C 2 02114011 4. Fluorescent agents which in the form of the alkylamino in which the alkyl group has from free acids have the formula 118 alkyl carbon atoms, secondary alkylamino 5. Fluorescent agents which in the form of the in which the alkyl groups have 1-5 alkyl carbon free acids have the formula atoms, primary monocyclic arylamino, N-alkyl- 6. A compound which in the form of the free anilino in which the alkyl group has from 1 to 4 acid has the formula alkyl carbon atoms and morpholine radicals and A W represents a member of the group consisting L of hydrogen, alkoxy, aryloxyl, alkyl, halogen, 4 as 50 cyano and trifluoroalkyl and Z represents a mem- 6 Q ber of the group consisting of COOH or SOaH.

c=N 1 Z WILLIAM W. WILLIAMS. WILLIAM E. WALLACE.

55 HARLAN B. FREYERMUTH. W CF I No references cited. 2 

6. A COMPOUND WHICH IN THE FORM OF THE FREE ACID HAS THE FORMULA 